CN115449215B - 3D printing wire rod and preparation method and application thereof - Google Patents

3D printing wire rod and preparation method and application thereof Download PDF

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Publication number
CN115449215B
CN115449215B CN202211173672.3A CN202211173672A CN115449215B CN 115449215 B CN115449215 B CN 115449215B CN 202211173672 A CN202211173672 A CN 202211173672A CN 115449215 B CN115449215 B CN 115449215B
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modified particles
printing wire
filler
resin matrix
printing
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CN115449215A (en
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赵俊恒
蒋铭波
郭晓晨
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Suzhou Multifilament Luoke New Materials Co ltd
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Suzhou Multifilament Luoke New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0078—Producing filamentary materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride

Abstract

The invention discloses a 3D printing wire rod, a preparation method and application thereof, wherein the 3D printing wire rod comprises an inner core layer and a coating layer coated on the inner core layer; the inner core layer is prepared by melt extrusion of modified particles A, and the raw materials of the modified particles A comprise: the resin comprises a first resin matrix, a filler, a compatilizer and a first antioxidant, wherein the first resin matrix accounts for more than 45%, the filler accounts for 30-45%, and the filler comprises a short fiber reinforced material; the coating layer is prepared by melt extrusion of modified particles B without filler, and the raw materials of the modified particles B comprise: the second resin matrix, tackifier, crystallization regulator and second antioxidant, the second resin matrix accounts for more than 80%; the 3D printing wire can solve the problem of wire toughness maintenance under the condition of adding high-content filler, and realizes the simultaneous consideration of the strength of a product manufactured by adopting an FDM process in the X-Y direction and the interlayer Z direction.

Description

3D printing wire rod and preparation method and application thereof
Technical Field
The invention relates to the field of plastic additive manufacturing processes, in particular to a 3D printing wire rod, a preparation method and application thereof.
Background
FDM (Fused Deposition Modeling), a melt lamination forming technique, sometimes called Cheng Rongsi, is used, with which plastic particles are typically processed into FDM strands (3D printed strands) that are fed into a 3D printer, the FDM strands are clamped by a pair of extrusion wheels in the 3D printer and fed into a heated die, typically 0.1-1mm in size, which is melted again after heating and extruded into filaments by a nozzle; the model file to be printed is processed by computer slicing software, the model file is sliced into slices along the horizontal X-Y direction according to the set thickness, the moving path of the spray head is planned on each layer, and the slice thickness is generally set to be about 1/2 of the size of the spray head. The 3D printer is provided with a X, Y and Z-direction moving mechanism, and the spray head is driven to move and extrude plastic wires according to a planned path of a computer slice during printing, and a physical model is obtained after printing is completed.
Currently, in the field of melt lamination extrusion type 3D printing (FDM) materials, more than 95% of the materials used are PLA (polylactic acid), PLA materials because of its T g 、T m The temperature is relatively low, and the method can be directly applied to the FDM process without modification basically. But PLA has poor heat resistance, and other materials, such as ABS, PA, PC, often have poor dimensional accuracy of printed samples due to too high shrinkage of the pure resin, and are prone to warp deformation, and the mechanical properties of the pure resin are poor, which limits the industrial application of 3D printing technology.
In the traditional injection molding industry, it is common practice to add short fiber fillers into a plastic formulation, and then process the mixture into FDM wires through a screw extruder after all blending, so as to improve the strength and heat resistance. However, based on performance requirements such as strength, a high filling amount of short fiber filler is required, however, with the continuous increase of the addition amount of the short fiber filler, the current FDM wire frequently breaks in the 3D printing process, and the printing failure occurs; the produced FDM wire is wound on a round wire coil in a coil mode, the existing high-filling wire is fragile, the wire coil shaft diameter is too small to be wound, only the wire coil with the larger shaft diameter can be replaced, and the packaging volume and the transportation cost of the product are increased in an intangible way; further, even after successful printing, the conventional FDM wire printed product also exhibits a problem that it is difficult to achieve both the X-Y direction strength and the interlayer Z direction strength.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art, and provides an improved 3D printing wire rod, which can solve the problem of toughness maintenance under the condition of adding high-content filler, and simultaneously solve the problem that the strength of a product manufactured by adopting the 3D printing wire rod for melt lamination extrusion type 3D printing in the X-Y direction and the strength of the product in the interlayer Z direction are simultaneously considered, so that the phenomenon of losing each other is avoided.
The invention also provides a preparation method of the 3D printing wire rod.
The invention also provides a 3D printing product which is manufactured by taking the 3D printing wire rod as a processing wire rod and printing by adopting a melt lamination extrusion type 3D printing method, and the strength of the product in the X-Y direction and the strength of the product in the interlayer Z direction can be simultaneously considered.
In order to achieve the above purpose, the invention adopts a technical scheme that:
a 3D printing wire, the 3D printing wire comprises an inner core layer and a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the raw materials of the modified particles A comprise: a first resin matrix, a filler, a compatibilizer, and a first antioxidant; the filler comprises a short fiber reinforced material, and in the raw material of the modified particle A, the first resin matrix accounts for more than 45% and the filler accounts for 30% -45% in percentage by mass;
the coating layer is prepared by melt extrusion of modified particles B without filler, and the raw materials of the modified particles B comprise: a second resin matrix, a tackifier, a crystallization regulator and a second antioxidant; and the second resin matrix accounts for more than 80% of the raw materials of the modified particles B in percentage by mass.
According to some preferred aspects of the invention, the first resin matrix is identical to the second resin matrix, and better encapsulation can be achieved based on similar compatibility principles.
In some embodiments of the present invention, the first resin matrix, the second resin matrix are each a combination of one or more selected from the group consisting of polyamide resin (PA), polyethylene terephthalate (PET), poly (ethylene terephthalate-1, 4-cyclohexanedimethylene terephthalate) (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), thermoplastic Polyurethane (TPU), polycarbonate (PC), polymethyl methacrylate (PMMA), and polyphenylene sulfide (PPS) and Polyetheretherketone (PEEK).
According to some preferred and specific aspects of the present invention, in the raw material of the modified particle a, the short fiber reinforcement material is a combination of one or more selected from the group consisting of short glass fibers, short carbon fibers, and basalt fibers.
In the invention, the raw material of the modified particle A can also contain at least one of flame retardant, antistatic agent, ultraviolet resistant agent, copper resistant agent and magnetic material, so as to realize the effects of flame retardance, antistatic and the like of the material.
According to some preferred aspects of the present invention, the compatibilizing agent is a reactive compatibilizing agent containing a reactive functional group that is capable of reacting with the first resin matrix, the reactive functional group comprising at least one of a maleic anhydride group, an epoxy group, an acrylic group, an amino group, and an isocyanate group.
According to a particular aspect of the invention, the compatibilizer is a maleic anhydride grafted ethylene octene copolymer (POE-g-MAH).
According to some preferred aspects of the present invention, the tackifier is a modified ethylene-vinyl acetate copolymer using at least one modifying group selected from the group consisting of a maleic anhydride group, an epoxy group, an acrylic group, an amino group and an isocyanate group.
According to a particular aspect of the invention, the tackifier is a maleic anhydride grafted ethylene-vinyl acetate copolymer (EVA-g-MAH).
According to some preferred aspects of the present invention, the crystallization modifier is at least one selected from the group consisting of calcium chloride, potassium chloride, zinc chloride, gallium chloride, sodium carboxylate, potassium carboxylate, calcium carboxylate, and ionic polymer.
According to the invention, the 3D printing wire is in a molten state, and the flow Reynolds number Re of the melt is 5-100; further, the flow Reynolds number Re of the melt is 5-20.
In some embodiments of the invention, the first antioxidant, the second antioxidant are each independently selected from the group consisting of antioxidant 1010, antioxidant 168, and the like.
According to some preferred and specific aspects of the present invention, the 3D printing wire has a diameter of 1.5 to 3.5mm, and the coating layer has a thickness of 0.05 to 0.30mm.
According to some preferred aspects of the invention, in the 3D printing wire, the thickness of the coating layer is 2.5% -18% of the diameter of the 3D printing wire. In some embodiments of the invention, the 3D printing wire has a diameter of 1.60-1.90mm or 2.75mm-3.0mm.
According to some preferred aspects of the present invention, in terms of mass percent, the raw materials of the modified particle a comprise 45% -65% of a first resin matrix, 30% -45% of a filler, 1% -15% of a compatibilizer, and 0.05% -1.0% of a first antioxidant;
the modified particles B comprise the following raw materials in percentage by mass: 75% -95% of a second resin matrix, 1% -15% of a tackifier, 1% -10% of a crystallization regulator and 0.05% -1.0% of a second antioxidant.
Further, in the raw materials of the modified particle A, 50-65% of a first resin matrix, 30-40% of a filler, 3-15% of a compatilizer and 0.05-1.0% of a first antioxidant are contained in percentage by mass;
the modified particles B comprise the following raw materials in percentage by mass: 78-90% of a second resin matrix, 5-15% of a tackifier, 1-8% of a crystallization regulator and 0.05-1.0% of a second antioxidant.
The invention provides another technical scheme that: the preparation method of the 3D printing wire comprises the following steps:
(1) After weighing each component in the raw materials of the modified particles A, putting other components except for the filler into a tail feeding port of a double-screw extruder, feeding the filler into the middle feeding port of the double-screw extruder, extruding, and granulating to obtain modified particles A;
weighing each component in the raw materials of the modified particles B, putting the raw materials into a tail feeding port of a double-screw extruder, extruding, and granulating to obtain modified particles B;
(2) And adding the modified particles A into an inner layer extruder, adding the modified particles B into an outer layer extruder, combining the inner layer extruder and the outer layer extruder, extruding through a coextrusion die head, and cooling the extruded wire through traction to obtain the 3D printing wire.
In the invention, the thickness of the inner layer and the outer layer and the diameter of the wire rod are controlled by adjusting the rotating speed and the traction speed of the screw rod of the extruder of the inner layer and the outer layer.
According to some preferred and specific aspects of the invention, the inner layer extruder processing temperature is 20-30 ℃ higher than the outer layer extruder.
The invention provides another technical scheme that: A3D printing product is manufactured by using the 3D printing wire rod as a processing wire rod and adopting a fusion lamination forming 3D printing method.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention innovatively provides a 3D printing wire rod with a coating structure, wherein the inner core layer of the 3D printing wire rod is made of a resin composition containing filler (containing a short fiber reinforced material), the coating layer is made of a resin composition containing no filler, and when the 3D printing wire rod is prepared in the mode, the invention finds that the addition amount of the filler can be obviously improved, the 3D printing wire rod basically does not have the problem of printing failure even if the addition amount is more than 30%, and a small-size wire coil can be adopted for winding; when the 3D printing wire is used as a processing wire of a fusion lamination forming technology, the printed product also shows excellent strength in the X-Y direction and the interlayer Z direction, and especially the interlayer Z direction strength can be higher than that of pure resin printing.
Drawings
FIG. 1 is a schematic diagram of a 3D printing process of melt lamination extrusion in an embodiment of the present invention;
wherein, 1, 3D prints the wire rod; 11. an inner core layer; 12. a coating layer; 2. an extrusion wheel; 3. a throat; 4. heating the die; 5. a spray head; 6. 3D prints the product.
Detailed Description
In the long-term practice process, the inventor finds that the 3D printing wire fails to print and the printed product cannot be wound by adopting a small-size shaft diameter wire coil based on a large amount of experimental researches, and the strength in the X-Y direction and the strength in the interlayer Z direction are difficult to be compatible, because of the following reasons: firstly, based on the characteristic of 3D printing, an extrusion wheel is required to clamp a wire rod to be fed into a heating die for melting, and the diameter of the 3D printing wire rod is usually only a few millimeters or smaller, so that in the process of clamping and conveying through the extrusion wheel, if the toughness of the wire rod is poor, the wire rod is easy to brittle fracture when being pulled by the extrusion wheel, and the probability of printing failure is increased; secondly, the 3D printing wire rod which is usually produced is wound on a round wire coil in a coil mode, if the wire rod is too fragile, the wire coil cannot be wound if the shaft diameter is too small, otherwise, the wire rod is easy to break in the winding process; thirdly, because the melt lamination extrusion molding mode is piled up layer by layer, when the lower plastic wires are cooled for a period of time, the surface temperature of the lower plastic wires may be cooled below the Tg temperature, the chain segment movement is stopped, the plastic wires which are just extruded from the upper layer are required to be transferred to the lower layer, the surface temperature of the lower layer is heated to be above the Tg temperature again to mutually generate chain segment movement, the chain segments on the surfaces of the upper layer and the lower layer are entangled together to form certain bonding strength, and for wires containing fillers or fibers, the larger the filling rate is, the contact area of high molecules among the extruded wires is smaller, and meanwhile, the capability of chain segment movement is blocked by the fibers, so that the interlayer strength of the wires with common fibers is far lower than that of pure resins without fillers or fibers.
Based on the above findings, the present invention innovatively proposes a 3D printing wire rod having a clad structure, and uniformly mixes a filler containing a short fiber reinforcement material (properties such as enhanced strength and heat resistance) as a blend phase in an inner core layer, and the clad layer contains no filler, so that the short fiber reinforcement material becomes a blend phase in a continuous phase of a resin matrix of the inner core layer in the 3D printing wire rod in practice by utilizing the characteristic that the filler, particularly the short fiber reinforcement material contained in the filler, can be uniformly oriented in a length direction of the wire rod during melt processing, and the short fiber reinforcement material does not protrude from the inner core layer based on the characteristic of uniform orientation, and realizes complete hiding of the short fiber reinforcement material inside after cladding with the clad layer having the resin matrix as a main material and containing no filler;
meanwhile, the inner core layer and the cladding layer of the invention are both made of resin matrix, so that the materials of the inner core layer and the cladding layer have higher melt viscosity in a molten state, the flow Reynolds number of the melt is basically below 100, when the resin content is further improved, the flow Reynolds number of the melt is basically below 50 and even basically between 5 and 20, the critical Reynolds number Re of a smooth circular tube channel in a 3D printer is about 2000-2300 and is far greater than the flow Reynolds number of the melt of the inner core layer and the cladding layer in the molten state, and then the flow of the inner core layer and the cladding layer in the pipeline of the 3D printer is basically in a laminar state, namely, the 3D printing wire with the cladding structure can still keep the relative independence of the inner core layer and the cladding layer and the stability of the mutual structure in the process of 3D printing of the molten lamination molding, the short fiber reinforced material contained in the inner core layer is not easy to migrate to the coating layer or even to the surface of the coating layer, so that the 3D printing wire rod is bonded with each other by pure resin in the process of fusion lamination forming 3D printing or in a manufactured product, the inter-molecular contact area is larger, therefore, the occurrence rate of chain segment movement and entanglement between the high molecular materials between adjacent layers is higher, and the short fiber reinforced material is always positioned in the inner core layer, and is subjected to the fusion processing process for preparing the 3D printing wire rod and the fusion processing process for preparing the 3D printing product, and is oriented for a plurality of times without protruding out of the inner core layer, so that when the layers are stressed, the force bearing is realized on the short fiber reinforced material which is easy to be conducted to the inner core layer, and the external acting force can be dispersed more uniformly, the prepared material or product has small overall shrinkage, and the deformation shrinkage is small when the material or product is finally cooled, and the intermolecular penetration entanglement state generated by the high temperature of the spray head in the early stage can be well reserved after cooling, so that the strength of the interlayer in the Z direction is obviously improved, and the strength of the material or product in the X-Y direction is also obviously improved; in addition, based on the conception of the invention, the 3D printing wire rod can be filled with more short fiber reinforced materials, realizes better heat resistance, does not basically influence the toughness of the materials, has high printing success rate and can be wound by adopting a small-size wire coil.
Further, based on the above concept, the present invention provides a 3D printing wire, which includes an inner core layer, a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the raw materials of the modified particles A comprise: a first resin matrix, a filler, a compatibilizer, and a first antioxidant; the filler comprises a short fiber reinforced material, and in the raw material of the modified particle A, the first resin matrix accounts for more than 45% and the filler accounts for 30% -45% in percentage by mass;
the coating layer is prepared by melt extrusion of modified particles B without filler, and the raw materials of the modified particles B comprise: a second resin matrix, a tackifier, a crystallization regulator and a second antioxidant; and the second resin matrix accounts for more than 80% of the raw materials of the modified particles B in percentage by mass.
The preparation of the 3D printing wire rod can be carried out by respectively preparing modified particles A and modified particles B, and then preparing the 3D printing wire rod with the coating structure by double-layer coextrusion. When a 3D printing product is required to be processed and prepared by adopting a fusion lamination forming 3D printing method, the preparation process is shown in figure 1, a 3D printing wire 1 with an inner core layer 11 and a coating layer 12 is clamped and driven by extrusion wheels 2 on the left side and the right side and is conveyed into a throat 3 of a 3D printer, then the 3D printing wire enters a heating mouth die 4 for heating and melting, filaments are extruded by a spray nozzle 5 after melting, a model file required to be printed is processed by computer slicing software, the model file is cut into slices along the horizontal X-Y direction according to the set thickness, a moving path of the spray nozzle is planned on each layer, the 3D printer is provided with a X, Y moving mechanism and a Z moving mechanism, the spray nozzle is driven to move and extrude plastic filaments according to the planned path of the computer slicing during printing, and a 3D printing product 6 is obtained after printing, and the plastic filaments in each layer of structure still show a coating structure.
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
PA12 was purchased from EMS Switzerland under the trademark Grilamid L20G;
the chopped carbon fiber is purchased from ZOLTEK and has the mark of PX35;
POE-g-MAH was purchased from Ke Aiss Chemie Co., ltd, under the designation W1A;
the crystallization regulator is calcium chloride, which is purchased from Tianjin gold hui taiya chemical reagent limited company and is of the grade of food;
the crystallization regulator is calcium carboxylate, which is purchased from special chemical product of Clariant and has the brand of Licom CaV102;
the crystallization regulator is an ionic polymer, and is purchased from the Dow chemical and has the brand Surlyn 1601;
EVA-g-MAH was purchased from Arkema, france under the trademark Orevac T9318;
antioxidant 1010 is available from BASF, germany under the trade name Irganox 1010;
chopped glass fibers were purchased from Taishan glass fiber Inc. under the trademark T435N;
PET is purchased from Huarun chemical materials science and technology Co., ltd, and the brand is CR-8839;
antioxidant 168 is available from BASF, germany under the trade name Irgafos 168;
PA6 was purchased from Jiangsu Ruimefu Co., ltd and is available under the trademark MF500.
Example 1
The embodiment provides a 3D printing wire, which comprises an inner core layer and a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the modified particles A comprise the following raw materials in percentage by mass:
the coating layer is prepared by melt extrusion of modified particles B without filler, and the modified particles B comprise the following raw materials in percentage by mass:
the preparation method of the 3D printing wire comprises the following steps:
(1) After weighing each component in the raw materials of the modified particles A, adding other components except for the filler into a tail feeding port of a double-screw extruder, feeding the filler into the double-screw extruder from a five-zone feeding port in the middle of the double-screw extruder, extruding and granulating, and obtaining the modified particles A at the rotating speed of 350rpm of the double-screw extruder;
twin screw zone temperatures:
weighing each component in the raw materials of the modified particles B, putting the raw materials into a tail feeding port of a double-screw extruder, extruding, granulating, and obtaining the modified particles B at the rotating speed of 250rpm of the double-screw extruder;
twin screw zone temperatures:
feed inlet Two-zone Three zones Four zones Five zones Six zones Seven areas Eight areas Nine zones Die head
160℃ 220℃ 240℃ 240℃ 240℃ 240℃ 240℃ 240℃ 240℃ 230℃
(2) Adding modified particles A into an inner layer extruder, adding modified particles B into an outer layer extruder, combining the inner layer extruder and the outer layer extruder, extruding in a coextrusion die head, and cooling the extruded wire by traction to obtain a 3D printing wire rod;
extrusion temperature of the coextrusion extruder:
wherein, by adjusting the screw rotation speed of the inner layer extruder and the outer layer extruder, the rotation speed of the inner layer extruder is 30rpm, the outer extruder speed was 20rpm and the draw speed was 65m/min. Controlling the thickness of the extrusion coating layer: 0.2mm, the diameter of the inner core layer is 1.35mm, and the diameter of the wire rod is 1.75mm.
The 3D printing wire made in this example was subjected to the following performance characterization while providing performance characterization of the wire made with modified particle a alone and the wire made with modified particle B alone, with specific results being seen in table 1.
TABLE 1
Note that: the test method is as follows:
z-axis interlayer tensile strength:
preparing a spline: GB/T1040I type sample, printing layer height 0.2mm, filling rate 100%, printing speed 45mm/s, printing temperature 280 ℃, bottom plate temperature 60 ℃.
Test standard: GB/T1040-2018
Tensile strength in X-Y axis:
preparing a spline: GB/T1040I type sample, printing layer height 0.2mm, filling rate 100%, printing speed 45mm/s, printing temperature 280 ℃, bottom plate temperature 60 ℃.
Test standard: GB/T1040-2018
Heat distortion temperature (1.80 MPa):
preparing a spline: spline size 80mm x 10mm x 4mm, print layer height 0.2mm, fill rate 100%, print speed 45mm/s, print temperature 280 ℃, floor temperature 60 ℃.
Test Standard GB/T1634-2004
100% fill shrinkage (X-Y and Z directions):
sample preparation: sample size 20mm, print layer height 0.2mm, fill rate 100%, print speed 45mm/s, print temperature 280 ℃, floor temperature 60 ℃.
Test standard: and measuring the actual sizes of the sample in the X-Y direction and the Z direction after printing by using a vernier caliper respectively, and calculating the shrinkage rate.
Minimum wire-windable coil diameter:
hard paper cylinders with different diameters are used, the length of the hard paper cylinder is 150mm, and the hard paper cylinder is fixed on a winding machine shaft. 1.75mm wire is inserted into one end of the cylinder for fixation, the winding speed is set to 80m/min, the wire is tightly arranged on the cylinder and is wound by 120mm, and brittle failure is avoided, namely the wire passes the winding test. If brittle fracture occurs, the diameter of the cylinder needs to be enlarged, and the steps are repeated until the wires can be tightly arranged and wound to be full of the cylinder by 120mm (the thickness is along the radial direction of the hard paper cylinder).
Example 2
The embodiment provides a 3D printing wire, which comprises an inner core layer and a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the modified particles A comprise the following raw materials in percentage by mass:
the coating layer is prepared by melt extrusion of modified particles B without filler, and the modified particles B comprise the following raw materials in percentage by mass:
the preparation method of the 3D printing wire comprises the following steps:
(1) After weighing each component in the raw materials of the modified particles A, adding other components except for the filler into a tail feeding port of a double-screw extruder, feeding the filler into the double-screw extruder from a feeding port in the middle of four areas, granulating after extrusion, and obtaining the modified particles A at the rotating speed of 350rpm of the double-screw extruder;
twin screw zone temperatures:
weighing each component in the raw materials of the modified particles B, putting the raw materials into a tail feeding port of a double-screw extruder, extruding, granulating, and obtaining the modified particles B at the rotating speed of 250rpm of the double-screw extruder;
feed inlet Two-zone Three zones Four zones Five zones Six zones Seven areas Eight areas Nine zones Die head
220℃ 240℃ 260℃ 280℃ 280℃ 280℃ 280℃ 280℃ 260℃ 260℃
(2) Adding modified particles A into an inner layer extruder, adding modified particles B into an outer layer extruder, combining the inner layer extruder and the outer layer extruder, extruding in a coextrusion die head, and cooling the extruded wire by traction to obtain a 3D printing wire rod;
wherein, the screw rotation speed of the inner layer extruder, the inner layer extruder rotation speed of 38rpm, the outer layer extruder rotation speed of 12rpm and the traction speed of 70m/min are adjusted. Controlling the thickness of the extrusion coating layer: 0.1mm, the diameter of the inner core layer is 1.55mm, and the diameter of the wire rod is 1.75mm.
The 3D printing wire made in this example was subjected to the following performance characterization while providing performance characterization of the wire made with modified particle a alone and the wire made with modified particle B alone, with specific results being seen in table 2.
TABLE 2
Example 3
The embodiment provides a 3D printing wire, which comprises an inner core layer and a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the modified particles A comprise the following raw materials in percentage by mass:
the coating layer is prepared by melt extrusion of modified particles B without filler, and the modified particles B comprise the following raw materials in percentage by mass:
the preparation method of the 3D printing wire comprises the following steps:
(1) After weighing each component in the raw materials of the modified particles A, putting other components except chopped glass fibers and flame retardants into a tail feeding port of a double-screw extruder, feeding the chopped glass fibers into the double-screw extruder from a feeding port in the middle four regions, feeding the flame retardants into the double-screw extruder from a feeding port in the five regions, granulating after extrusion, and obtaining the modified particles A at the rotating speed of 250rpm of the double-screw extruder;
twin screw zone temperatures:
weighing each component in the raw materials of the modified particles B, putting the raw materials into a tail feeding port of a double-screw extruder, extruding, granulating, and obtaining the modified particles B at the rotating speed of 250rpm of the double-screw extruder;
(2) Adding modified particles A into an inner layer extruder, adding modified particles B into an outer layer extruder, combining the inner layer extruder and the outer layer extruder, extruding in a coextrusion die head, and cooling the extruded wire by traction to obtain a 3D printing wire rod;
wherein, the screw rotation speed of the inner layer extruder and the outer layer extruder is adjusted, the rotation speed of the inner layer extruder is 39rpm, the rotation speed of the outer layer extruder is 10rpm, and the traction speed is 70m/min. Controlling the thickness of the extrusion coating layer: 0.08mm, inner core layer diameter 1.59mm, wire diameter 1.75mm.
The 3D printing wire made in this example was subjected to the following performance characterization while providing performance characterization of the wire made with modified particle a alone and the wire made with modified particle B alone, with specific results being seen in table 3.
TABLE 3 Table 3
Comparative example 1
Example 1 the wire diameter was 1.75mm and the coating layer thickness was 0.2mm, modified particle A and the change could be calculatedThe linear particles B occupy a wire volume ratio of about 1.47:1. The density of the modified A particles is 1.35g/cm 3 Modified particles B having a density of 1.12g/cm 3 . The weight ratio of modified particle a to modified particle B to the interior of the coated wire is about 2.22:1.
This comparative example is basically the same as example 1, and differs only in that: mixing modified particles A and modified particles B according to a weight ratio of 2.22:1, extruding by a single screw extruder, wherein the extruding speed is 38rpm, and the traction speed is 60m/min, so as to prepare the common uncoated wire rod with the diameter of 1.75mm.
The processed wire rods produced in this example were characterized as follows and compared with example 1, with specific results shown in Table 4.
TABLE 4 Table 4
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

Claims (11)

1. The 3D printing wire is characterized by comprising an inner core layer and a coating layer coated on the inner core layer;
the inner core layer is prepared by melt extrusion of modified particles A, and the raw materials of the modified particles A comprise: a first resin matrix, a filler, a compatibilizer, and a first antioxidant; the filler comprises a short fiber reinforced material, and in the raw material of the modified particle A, 45-65% of a first resin matrix, 30-45% of the filler, 1-15% of a compatilizer and 0.05-1.0% of a first antioxidant are contained in percentage by mass;
the coating layer is prepared by melt extrusion of modified particles B without filler, and the raw materials of the modified particles B comprise: a second resin matrix, a tackifier, a crystallization regulator and a second antioxidant; in the raw materials of the modified particles B, the second resin matrix accounts for 75-95 percent, the tackifier accounts for 1-15 percent, the crystallization regulator accounts for 1-10 percent and the second antioxidant accounts for 0.05-1.0 percent;
the flow Reynolds number Re of the melt of the 3D printing wire is 5-100 in the melt state;
the tackifier is a modified ethylene-vinyl acetate copolymer, and the modified group adopted by the modified ethylene-vinyl acetate copolymer is at least one selected from maleic anhydride groups, epoxy groups, acrylic acid groups, amino groups and isocyanate groups.
2. The 3D printing wire according to claim 1, wherein the first resin matrix is the same as the second resin matrix.
3. The 3D printing wire according to claim 2, wherein the first resin matrix and the second resin matrix are each a combination of one or more selected from a polyamide resin, polyethylene terephthalate, poly (ethylene terephthalate-1, 4-cyclohexadiene dimethylene terephthalate), acrylonitrile-butadiene-styrene copolymer, thermoplastic polyurethane, polycarbonate, polymethyl methacrylate, polyphenylene sulfide, and polyether ether ketone.
4. The 3D printing wire according to claim 1, wherein in the raw material of the modified particle a, the short fiber reinforcement material is a combination of one or more selected from the group consisting of short glass fiber, short carbon fiber and basalt fiber;
and/or the raw materials of the modified particles A, wherein the filler also comprises at least one of flame retardant, antistatic agent, ultraviolet resistant agent, copper resistant agent and magnetic material.
5. The 3D printing wire according to claim 1, wherein the compatibilizer is a reactive compatibilizer that contains a reactive functional group and is capable of reacting with the first resin matrix, the reactive functional group including at least one of a maleic anhydride group, an epoxy group, an acrylic group, an amino group, and an isocyanate group;
the crystallization regulator is one or a combination of more selected from calcium chloride, potassium chloride, zinc chloride, gallium chloride, sodium carboxylate, potassium carboxylate, calcium carboxylate and ionic polymer.
6. The 3D printing wire according to claim 1, wherein the 3D printing wire has a melt flow reynolds number Re of 5-20 in a molten state.
7. The 3D printing wire according to claim 1, wherein the diameter of the 3D printing wire is 1.5-3.5mm, and the thickness of the coating layer is 0.05-0.30mm.
8. The 3D printing wire according to claim 1 or 7, wherein in the 3D printing wire, the thickness of the coating layer is 2.5% -18% of the diameter of the 3D printing wire.
9. The 3D printing wire according to claim 8, wherein the modified particle a comprises, in mass percent, 50% -65% of a first resin matrix, 30% -40% of a filler, 3% -15% of a compatilizer, and 0.05% -1.0% of a first antioxidant;
the modified particles B comprise the following raw materials in percentage by mass: 78-90% of a second resin matrix, 5-15% of a tackifier, 1-8% of a crystallization regulator and 0.05-1.0% of a second antioxidant.
10. A method of producing the 3D printing wire according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
(1) After weighing each component in the raw materials of the modified particles A, putting other components except for the filler into a tail feeding port of a double-screw extruder, feeding the filler into the middle feeding port of the double-screw extruder, extruding, and granulating to obtain modified particles A;
weighing each component in the raw materials of the modified particles B, putting the raw materials into a tail feeding port of a double-screw extruder, extruding, and granulating to obtain modified particles B;
(2) And adding the modified particles A into an inner layer extruder, adding the modified particles B into an outer layer extruder, combining the inner layer extruder and the outer layer extruder, extruding through a coextrusion die head, and cooling the extruded wire through traction to obtain the 3D printing wire.
11. A 3D printed product, characterized in that the 3D printed product is manufactured by using the 3D printed wire rod according to any one of claims 1 to 9 as a processing wire rod by a melt lamination forming 3D printing method.
CN202211173672.3A 2022-06-10 2022-09-26 3D printing wire rod and preparation method and application thereof Active CN115449215B (en)

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